CN103370357A

CN103370357A - Method for producing polyether ester polyols

Info

Publication number: CN103370357A
Application number: CN2011800675660A
Authority: CN
Inventors: K·劳伦斯; J·霍夫曼; B·科雷兹尤斯基; N·哈恩
Original assignee: Bayer Pharma AG
Current assignee: Bayer Pharma AG; Bayer Intellectual Property GmbH
Priority date: 2010-12-20
Filing date: 2011-12-19
Publication date: 2013-10-23
Also published as: EP2655475A1; JP2014501826A; KR20140007822A; SG190873A1; WO2012084760A1; US20140329985A1

Abstract

The invention relates to a method for producing polyether ester polyols on the basis of renewable resources, to the polyether ester polyols produced using the method according to the invention, to the use thereof for producing polyurethanes, and to polyurethanes containing the polyether ester polyols according to the invention.

Description

The method for preparing polyester ether polylol

The invention provides a kind of for the preparation of based on the method for renewable raw-material polyester ether polylol, the polyester ether polylol that can obtain by the inventive method, with and for the preparation of the purposes of urethane purpose.Polyester ether polylol based on renewable starting material (for example fatty acid glyceryl ester, sugar, Sorbitol Powder, glycerine and Fatty Alcohol(C12-C14 and C12-C18) dipolymer) is used in the preparation of urethane in every way as starting material.From now on, the use of these components will further increase, because have favourable value from the product of renewable resources in the eubiosis, and will descend based on the availability of raw materials of petroleum chemicals in the long run.

In polyurethane formulations, use as sugar, glycerine and the Sorbitol Powder of polyol component and oligose or saccharan increases, and is subject on the one hand them and is usually used in polyether glycol or the low-solubility in the polyester polyol and the with it restriction of high uncompatibility in the polyurethane chemistry at other; On the other hand, because their high-density of oh group, so these materials even in the situation that low dosage is also adversely given polyol component with higher OH value.

Fatty acid glyceryl ester obtains from renewable resources in a large number, so it has consisted of the raw-material cheap basis of urethane.Especially in rigid foam (rigid-foam) prescription, this compounds has following feature: just have higher dissolving power with regard to the pneumatogen of hydro carbons.A shortcoming is only to have few fatty acid glyceryl ester to demonstrate for the necessary active hydrogen atom of isocyanate conversion.Exception has Viscotrol C and rare Leix gram to strangle oil (Lesquerella oil).Yet the availability of Viscotrol C is owing to the cultivated area of limited space is restricted.

The uncompatibility that another is its and other polyol component about problem of using tri-glyceride in foam formulation---especially and polyether glycol---.

In the situation of prior art, proposed certain methods and solved the problems referred to above:

DE-C 33 23 880 and WO-A 2004/20497 relate to using DMC catalysts in the alkylene oxide adduct based on assigning to prepare from the initial set of renewable resources, its objective is to make it be applicable to polyurethane chemistry.As preferred starting ingredient, often use Viscotrol C; Also available subsequently by the oil of oh group modification.According to disclosed method, can obtain the polyester ether polylol of relative high molecular.Yet, employed tri-glyceride, unless use Viscotrol C, otherwise must be by the oh group modification in an independent reactions steps.

According to US-B 6,420,443, be used for expanding material based on the whipping agent of hydrocarbon and can be added to hydroxylated tri-glyceride by epoxy alkane and obtain.In a similar manner, in DE-A 101 38 132, described and to be used for the polyurethane system of dead-soft matter by the OH adducts that Viscotrol C or hydroxylated fatty acid cpds and epoxy alkane form as hydrophobic components.

US-B 6,686,435, EP-A 259722, US-B 6,548,609, US-A 2003/0088054, US-A 6,107,433, DE-A 36 30 264, US-A 2,752,376, US-B 6,686,435 and WO 91/05759 purposes of product in polyurethane system that disclose the open loop of epoxidised derivative of fatty acid and obtained.The remarkable shortcoming of all these methods is that epoxide group must be generated by two keys of fatty acid residue in the upstream reaction step.

WO-A 2004/096744 discloses and has been used for undersaturated fatty acid ester hydroxylation and methylolated method, has instructed among the WO-A 2004/096882 it is further transformed to form the condenses of branching by transesterify.WO-A 2004/096883 has presented these condensess that contains the OH group has been used for the flexible foam prescription.

US-B 6,359, and 022 discloses as the hydrophobic components of the OH component in the rigid foam prescription such as the ester exchange offspring of tri-glyceride, phthalic acid derivatives and polyvalent alcohol, and described rigid foam prescription uses alkane as whipping agent.The polyether glycol of choosing extra use in polyol component wantonly must prepare in an independent reactions steps.EP-A 905 158 discloses the whipping agent emulsion adjuvant that is used for based on the rigid foam prescription of the esterification products of the derivative of lipid acid and alcohol or ester exchange offspring.EP-A 610 714 has instructed by following with the derivative of fatty acid of OH official's energy and the esterification products of low-molecular-weight polyvalent alcohol and has prepared hydrophobic hard polyurethane foams.

WO-A 2006/040333 and WO-A 2006/040335 disclose the saccharan of hydrophobically modified, its by obtain with fatty acid esterification, with and in the flexible foam prescription, be used as the purposes that increases the compressive strength component.

DE-A 196 04 177 described Viscotrol C or hydroxylated tri-glyceride and polyfunctional initial alcohol the epoxy alkane adduct transesterify with and in the preparation of the solids system of solidifying in still mode as the purposes of component stable in storage.

DE-A 199 36 481 discloses the component of long-chain Viscotrol C Aethoxy Sklerol as preparation sound absorption flexible foam.The preparation condition of Viscotrol C Aethoxy Sklerol is not disclosed.

According to the instruction of EP-A 1 923 417, being applicable to polyvalent alcohol that urethane uses can be by the acquisition that is converted simultaneously under alkaline condition with the initiator of active hydrogen atom and tri-glyceride and epoxy alkane.As the key advantages of the method, the oil in the various plant and animals source that requires emphasis all is suitable for the method.Especially, it is suitable for not having in fatty acid residue the tri-glyceride of hydroxyl to be converted into the polyvalent alcohol that has from the component of renewable resources.Method claimed in EP-A 1 923 417 has been described in detail in EP-A 2 028 211 and WO-A 2009/106244, and the purpose of these two documents is further to simplify the regenerative process of these polyester ether polylols.A shortcoming of the method for describing in EP-A 1 923 417, EP-A 2 028 211 and WO-A 2009/106244 is because basic reaction conditions, transesterify continues to the end of epoxy alkane addition stage, therefore obtains the product of polyethers chain length non-uniform Distribution.Therefore, at EP-A 1 923 417, polyester ether polylol claimed among EP-A 2 028 211 and the WO-A 2009/106244 preferably is suitable for preparing hard polyurethane foam, and is unsuitable for preparing polyurethane flexible foam.

Therefore, the purpose of this invention is to provide a kind of for the preparation of the simple method based on renewable raw-material polyester ether polylol.The purpose of---particularly flexible foam---in order to prepare urethane, polyester ether polylol prepared in accordance with the present invention can be with doing the isocyanic ester active component that responds, and can avoid the shortcoming according to the polyester ether polylol for preparing based on renewable raw-material prior art present situation.Especially, the method does not need the step as filtering, processing with sorbent material or ion-exchanger.

Surprisingly, this purpose is achieved by a kind of method for preparing based on reproducible raw-material polyester ether polylol (1), the OH value of described polyester ether polylol (1) is 3mg to less than component A) the OH value, preferred 3mg to 120mg KOH/g, 14mg to 75mg KOH/g particularly preferably is characterized in that:

(i) have at least 70mg KOH/g, preferred 130mg to 500mg KOH/g, particularly preferably the component A of the OH value of 180mg to 300mg KOH/g) prepare by following steps:

(i-1) in the presence of basic catalyst, H-official can initial compounds A1) with one or more fatty acid esters A2) and with one or more epoxy alkane A3) transform, the concentration of contained basic catalyst is 40ppm to 5000ppm, with respect to component A) the total mass meter, and subsequently

(i-2) with the product of sulfuric acid neutralization from step (i-1), be characterised in that the catalyzer that uses in every mole of step (i-1) uses 0.75mol to 1mol sulfuric acid, and be characterised in that the salt that produces is retained in component A in this process) in, and

(i-3) randomly, at the trace water of under 20 ℃ to 200 ℃, preferred 80 ℃ to 180 ℃ temperature, removing reaction water under 1 millibar to 500 millibars the absolute pressure and introducing along with acid,

(ii) subsequently in double metal cyanide (DMC) catalyst B 2) in the presence of with component A) with one or more epoxy alkane B1) transform.

Other themes of the present invention also have the polyester ether polylol for preparing by method of the present invention with and for the preparation of the purposes of urethane purpose, particularly it is for the preparation of the purposes of polyurethane flexible foam purpose, and the urethane that contains polyester ether polylol of the present invention.

Below will describe method of the present invention in detail:

Step (i)

（i-1）

In one embodiment of the invention, in step (i-1), in reactor, add the initial compounds A1 of H-official's energy), with itself and basic catalyst and one or more fatty acid esters A2) and one or more epoxy alkane A3) mix.

Component A with respect to acquisition in step (i)) amount meter, fatty acid ester A2) preferably use with the amount of 10wt.% to 75wt.%.If if in adding the process of basic catalyst, produce water or in the process that adds basic catalyst, be introduced as concomitantly the water of solvent, then preferably adding one or more fatty acid esters A2) before except anhydrating, this process is under 20 ℃ to 200 ℃ the temperature, preferably under 80 ℃ to 180 ℃ temperature, in the vacuum of 1 millibar to 500 millibars absolute pressure and/or by carrying out with inert gas purge.In using the process of inert gas purge, by making rare gas element by liquid phase and using simultaneously 5 millibars of vacuum to 500 millibars of absolute pressures and remove volatiles.This also adopts to stir under preferred 80 ℃ to 180 ℃ temperature and carries out advantageously 20 ℃ to 200 ℃ temperature.

Fatty acid ester A2 with regard to meaning of the present invention) with regard to, should understand glycerin fatty acid ester, particularly fatty acid glyceryl ester, and/or the ester with lipid acid of the alkoxide component that comprises simple function and/or polyfunctional alcohol have 〉=32g/mol is to the molecular weight of≤400g/mol.For example, for Viscotrol C, fatty acid ester also can be with the fatty acid residue of hydroxyl group.In the method for the invention, also can use fatty acid ester, its fatty acid residue is subsequently by the oh group modification, for example by epoxidation or open loop or atmospheric oxidation.

All fatty acid glyceryl esters all are suitable as the matrix of the inventive method.Can specify following material in the mode of example: cotton seed oil, peanut oil, Oleum Cocois, linseed oil, palm-kernel oil, sweet oil, Semen Maydis oil, plam oil, Viscotrol C, Leix gram are strangled oil, rapeseed oil, soya-bean oil, Trisun Oil R 80, pilchardine, sardine oil and tallow oil.Also can use in the method for the invention on the fatty acid ester of other simple functions or polyfunctional alcohol and each the glyceryl ester molecule with the glycerol fatty acid ester that is less than three fatty acid residues.Can also mix the fatty acid ester that uses fatty acid glyceryl ester, glycerin fatty acid ester and other simple functions or polyfunctional alcohol.

The simple function or the polyfunctional alcohol that are suitable as the fatty acid ester composition can be---being not limited to these---alkanol, cycloalkanol and/or Aethoxy Sklerol.Example is n-hexyl alcohol, n-dodecane is pure, Octadecane is pure, hexalin, 1,4-dihydroxyl hexalin, 1, ammediol, 2-methyl isophthalic acid, ammediol, 1,5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, neopentyl glycol, Diethylene Glycol, triethylene glycol, TEG, dipropylene glycol, tripropylene glycol, dibutylene glycol, glycerine and/or TriMethylolPropane(TMP).Thus, preferred 1,3-PD, 1,5-PD, 1,6-hexylene glycol, neopentyl glycol, Diethylene Glycol, triethylene glycol and/or TriMethylolPropane(TMP).The boiling point that specified alcohol presents can be avoided discharging with reaction water, and does not also have the tendency of unwanted side reaction under common temperature of reaction.

Method of the present invention is suitable for making the fatty acid ester that does not contain the OH group in fatty acid residue to be converted into needed polyester ether polylol particularly well, described fatty acid residue is, for example based on lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, Zoomeric acid, oleic acid, erucic acid, linolic acid, linolenic acid, eleostearic acid, arachidonic fatty acid ester or its mixture.Particularly preferably as fatty acid ester A2) be based on oleic acid, erucic acid, linolic acid, linolenic acid, elaidic acid and arachidonic tri-glyceride; Be suitable as most fatty acid ester A2) be soya-bean oil.

Can use alkali metal hydroxide, alkali and alkaline earth metal ions hydride, alkali and alkaline earth metal ions carboxylate salt or alkaline earth metal hydroxides as basic catalyst.Basic metal is selected from Li, Na, K, Rb, Cs, and alkaline-earth metal is selected from Be, Ca, Mg, Sr, Ba.In these catalyzer, the preferred as alkali compound; Alkali metal hydroxide particularly preferably; Potassium hydroxide quite particularly preferably.The catalyzer of this alkali metal containing can be used as the aqueous solution or solid matter is supplied with H-official's energy initial compounds.Equally, can use for example amine of organic basic catalyzer.It comprises aliphatic amine or alkanolamine, N for example, N-dimethyl benzylamine, dimethylaminoethanol, dimethylamino propyl alcohol, N methyldiethanol amine, Trimethylamine 99, N, N-dimethylcyclohexylamine, N-ethyl pyrrolidine, N, N, N ', N '-tetramethylethylened, diazabicyclo [2,2,2] octane, Isosorbide-5-Nitrae-lupetazin or N-methylmorpholine.Also available have an arylamine, for example the imdazole derivatives, DMA, 4-(N, the N-dimethyl) aminopyridine that replace of imidazoles and alkyl and the partial cross-linked multipolymer that is formed by 4-vinylpridine or vinyl imidazole.M.Ionescu et al. ' Advances in Urethanes Science and Technology ' has provided the summary of catalytic activity amine among 1998,14, the 151-218.The concentration of catalyzer is with respect to step I) in the component A that obtains) amount count the amount of 40ppm to 5000ppm, preferred 40ppm to 1000ppm, particularly preferably 40ppm to 700ppm.At 1 millibar to the vacuum of 500 millibars of absolute pressures, at 20 ℃ to 200 ℃, under preferred 80 ℃ to the 180 ℃ temperature, aqueous solvent and/or the water that discharges in the reaction process of H-official's energy initial compounds and catalyzer can be removed before one or more epoxy alkane of metering begin or before adding one or more fatty acid esters.

As basic catalyst, also can use can initial compounds with the H-official of the alkoxide content of 0.05 equivalent % to 50 equivalent % prefabricated epoxy alkane adduct---so-called ' alkoxide of polymerization '.The alkoxide content of catalyzer is interpreted as the active hydrogen atom removed by deprotonation by alkali (being generally alkali metal hydroxide) and initially has been present in the ratio of the active hydrogen atom in the epoxy alkane adduct of catalyzer with respect to all.Certainly, describe such as leading portion, the consumption of polymeric alkanones oxide compound depends on the component A that obtains in the step (i)) catalyst concn of making every effort to.

As the polymeric alkanones oxide compound of catalyzer can be in independent reactions steps epoxy alkane by base catalysis join suitable H official and can prepare by initial compounds.For example, in the preparation process of polymeric alkanones oxide compound, use basic metal or alkaline earth metal hydroxides (for example KOH) as catalyzer, its amount with respect to the amount meter of polymeric alkanones oxide compound to be prepared is 0.1wt.% to 1wt.%, reaction mixture is under 1 millibar to 500 millibars absolute pressure, at 20 ℃ to 200 ℃, dewater under preferred 80 ℃ to the 180 ℃ temperature, under 100 ℃ to 150 ℃ temperature, in inert gas atmosphere, carry out the epoxy alkane addition reaction until obtain the OH value of 150mg to 1200mgKOH/g, then by adding other alkali metal or alkaline earth metal hydroxides and dehydration subsequently, above-mentioned alkoxide content is set as 0.05 equivalent % to 50 equivalent %.The polymeric alkanones oxide compound of preparation can store separately under inert gas atmosphere by this way.Found that for a long time they can be applicable in the preparation of long-chain polyether polyols.The amount of the polymeric alkanones oxide compound that uses among the present invention makes it corresponding to the amount of basic metal or alkaline earth metal hydroxides usually, with respect to the component A that obtains in the step (i)) quality count 40ppm to 0.5wt%.In the method, the polymeric alkanones oxide compound can also use by mixture.

Before reality is implemented method of the present invention, also can in same reactor, carry out the preparation of polymeric alkanones oxide compound by direct in-situ.In this case, the amount for the necessary polymeric alkanones oxide compound of polymerization charge generates according to the described step of leading portion in reactor.Use this step, the amount heat that should make described compound be stirred and to react that can initial compounds the H-official of the beginning of reaction can dissipate.This can choose wantonly by inert solvent such as toluene and/or THF are joined in the reactor (in case for this H-official can initial compounds amount too small) realize.

H-official's energy initial compounds A1) for containing the compound of at least one hydrogen atom that is connected with N, O or S.If described hydrogen produces as the methane with methyl magnesium iodide conversion results by the method for being found by Tserevitinov, then these hydrogen atoms also can be called as Tserevitinov active hydrogen (sometimes also only being called ' active hydrogen ').The representative instance that contains the compound of Tserevitinov active hydrogen is the compound that contains carboxyl, hydroxyl, amino, imino-or thiol group as functional group.

The H-official's energy initial compounds A1 that is fit to) mainly presents 1 to 35, preferred 1 to 8 functionality.Their molar mass adds up to 17g/mol to 1200g/mol.Except the initiator of the hydroxyl-functional of preferred use, also can use the initiator of amino-functional.The example of the initial compounds of hydroxyl-functional is methyl alcohol, ethanol, the 1-propyl alcohol, 2-propyl alcohol and higher aliphatic single methanol, Fatty Alcohol(C12-C14 and C12-C18) particularly, phenol, the phenol that alkyl replaces, propylene glycol, ethylene glycol, Diethylene Glycol, dipropylene glycol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, hexylene glycol, pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 1,12-dodecyl alcohol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder, sucrose, quinhydrones, pyrocatechol, Resorcinol, Bisphenol F, dihydroxyphenyl propane, 1,3,5-trihydroxybenzene, and the condenses that contains methylol groups that is formed by formaldehyde and phenol or urea.Also can use the initial compounds based on high official's energy of hydrated starch hydrolysate.These compounds for example are recorded among the EP-A 1 525 244.The example of H-official's energy initial compounds of the amido-containing group that is fit to is ammonia, thanomin, diethanolamine, trolamine, α-amino isopropyl alcohol, diisopropanolamine (DIPA), quadrol, hexamethylene-diamine, hexahydroaniline, diamino-cyclohexane, isophorone diamine, 1, the isomer of 8-p-diamino methane, aniline, the isomer of Tolylamine, the isomer of diaminotoluene, the product of the isomer of diaminodiphenyl-methane and the higher nuclear that produces in the process that forms diaminodiphenyl-methane at aniline and formaldehyde condensation also has the condenses that contains methylol groups that is formed by formaldehyde and trimeric cyanamide and Mannich base.In addition, the open-loop products that is formed by cyclic carboxylic acids acid anhydride and polyvalent alcohol also can be used as initial compounds.Example is on the one hand by Tetra hydro Phthalic anhydride, succinyl oxide, maleic anhydride, on the other hand by ethylene glycol, Diethylene Glycol, 1,2-butyleneglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, hexylene glycol, pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 1, the open-loop products that 12-dodecyl alcohol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane or Sorbitol Powder form.In addition, also can use simple function or polyfunctional carboxylic acid directly as initial compounds.

In addition, also can be with the prefabricated epoxy alkane adduct of aforementioned initial compounds, namely preferably with the OH value of 160mg to 1000mg KOH/g, the polyether glycol of preferred 250mg to 1000mg KOH/g joins in present method.Also can use preferably polyester polyol with the OH value in 6mg to 800mg KOH/g scope as the common initiator in the inventive method for preparing the polyether ester purpose.For this, suitable polyester polyol for example can be by with the organic dicarboxylic acid of 2-12 carbon atom and by with 2-12 carbon atom, and the polyhydroxy-alcohol (preferred diol) of preferred 2-6 carbon atom prepares by known method.

In addition, can be with polycarbonate polyol, polyestercarbonate polyvalent alcohol or the polyether carbonate polyol that preferably has separately the OH value in 6mg to the 800mg KOH/g scope, optimization polycarbonate glycol, polyestercarbonate glycol or polyether carbonate glycol be as H-official's energy initial compounds A1) common initiator.It is for example by phosgene, methylcarbonate, diethyl carbonate or diphenyl carbonate and two senses or the alcohol of higher official energy or the preparation that is converted of polyester polyol or polyether glycol.

In the method for the invention preferably will with the H-official of the not amido-containing group of hydroxyl can initial compounds as the carrier of active hydrogen, methyl alcohol for example, ethanol, the 1-propyl alcohol, 2-propyl alcohol and higher aliphatic single methanol, Fatty Alcohol(C12-C14 and C12-C18) particularly, phenol, the phenol that alkyl replaces, propylene glycol, ethylene glycol, Diethylene Glycol, dipropylene glycol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, hexylene glycol, pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 1,12-dodecyl alcohol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder, sucrose, quinhydrones, pyrocatechol, Resorcinol, Bisphenol F, dihydroxyphenyl propane, 1,3,5-trihydroxybenzene, the condenses that contains methylol groups that is formed by formaldehyde and phenol and the hydrolysate of hydrated starch.Wherein, preferred functionality is more than or equal to 4 initial compounds, for example tetramethylolmethane, Sorbitol Powder and sucrose again.Also can use the mixture of these initial compounds.

In step (i-1), under inert gas atmosphere under 80 ℃ to 180 ℃, preferred 100 ℃ to 170 ℃ temperature, with H-official can initial compounds A1) drop in the reactor and cause one or more fatty acid esters A2 with catalyzer) and with one or more epoxy alkane A3) reaction, epoxy alkane adds in the reactor in a conventional manner continuously, in this way so that be no more than the safe pressure boundary of employed reactor assembly.Especially in the epoxy alkane mixture that contains oxyethane or process that pure ethylene oxide is metered into, it is careful to guarantee keeping enough rare gas element dividing potential drops in reactor in initial sum is metered into the process in stage to need.This pressure can be regulated by for example rare gas or nitrogen.Certainly, be metered in the process in stage at epoxy alkane, temperature of reaction can change in described boundary: for H-official's energy initial compounds (such as sucrose) of sensitivity, advantageously at first under lower temperature of reaction, carry out alkoxylation, then only carry out alkoxylation in the situation that initiator fully transforms under higher temperature of reaction.Can epoxy alkane be fed in the reactor with different modes: can be metered in the gas phase or directly add in the liquid phase, for example by near the floodpipe the reactor bottom that is positioned at good hybrid region (immersion pipe) or current collector (ring manifold).In the situation that be metered into liquid phase, metering unit should be designed to from emptying, for example makes dip hatch and current collector bottom surface chimeric.Usually, should pass through the apparatus measure---for example, by vacuum breaker is installed---stop reaction medium to be back in the metering unit.If the mixture of epoxy alkane is metered into, then separately epoxy alkane can be supplied in the reactor separately or as mixture.For example, the pre-mixing of epoxy alkane can obtain by the mixed cell that is positioned at common metering section (' line blending (inline blending) ').It is favourable that the discharge side general epoxy alkane independent or premix that has also proved at pump is metered into circulation loop, and described adding circulation loop can for example be undertaken by heat exchanger.For with the well blend of reaction medium, it is favourable the high shear mixing unit being incorporated in the logistics of epoxy alkane and reaction medium.Make the temperature of addition reaction of the epoxy alkane of heat release maintain required level by cooling.According to the prior art present situation relevant with the polymerization reactor design that is used for thermopositive reaction (Ullmann ' s Encyclopedia of Industrial Chemistry for example, volume B4, after 167 pages, the 5th edition, 1992), such cooling passes usually that reactor wall (for example, double-walled chuck, semi-canal type coil) carries out and by carry out on the surface in the inside of reactor and/or at other heat exchangers---for example on spiral coil cooling tube, cooling stick, plate-type heat exchanger, shell and tube heat exchanger or direct contact heat exchanger---of circulation loop outer setting.These devices should design so that when initial in the stage that is metered in mode so---, have low fill level---also can effectively cool off.

Usually, should provide good mixing for the content of reactor by the commercially available agitation elements of design and use in whole step of reaction, herein, especially, with the agitator of one or more levels arrangement or act on type of stirrer on the big area of whole packing height be fit to (referring to, for example, Handbuch Apparate; Vulkan-Verlag Essen, the 1st edition (1990), 188-208 page or leaf).In this respect technical relevant especially be to have that corresponding higher local energy in the zone of agitation elements itself is inputted and the mixed tensor of lower charging level randomly, described mixed tensor is that it is usually located in the scope of 0.2W/l-5W/l by the average input of the entire contents of reactor.In order to obtain best stirring action, according to the usual condition of prior art, baffle plate (for example, flat or tubular type baffle plate) and the combination of spiral coil cooling tube (or cooling stick) can be arranged in the reactor, extend its bottom that also can prolong container.Also can change at the power of agitator with the mixed cell in the process of the metering phase of the dependent mode of fill level, thereby guarantee in the step of reaction of key extra high energy input is arranged.For example, in the situation that for example use sucrose, the dispersion---it can be present in the initial stage of reaction---that special tempestuously mixing contains solid is favourable.In addition, especially for the initial compounds that uses solid H-official energy, should guarantee by selecting agitating unit to guarantee the abundant dispersion of solid matter in the reaction mixture.Preferred use herein is specially adapted to bottom purge agitation phases and the agitation elements of suspension.In addition, the geometrical shape of agitator should help to reduce the reaction product foaming.When further being removed under the vacuum of the absolute pressure of residual epoxy alkane in 1 millibar to 500 millibars scope, can observe the foaming of reaction mixture after the stage at for example metering and secondary reaction.For such situation, agitation elements has proved the continuous mixing that is fit to realize fluid surface.According to described demand, stir shaft is with bottom bearing and other optional steady bearings in container.In this case, the driving of stir shaft can produce (center of axle or centrifugal setting) by top or bottom.

Perhaps also can only obtain essential mixing by the circulation loop that carries out via heat exchanger, perhaps operate the loop as other electric hybrid modules except agitating unit, thus as required recirculation of the content of reactor (1-50 time/hour usually).

Most of dissimilar reactors are applicable to the enforcement of method of the present invention.Preferably, employing has height/diameter than being the cylindrical vessel of 1:1 to 10:1.For example sphere, torispherical, flat or conical bottom can be considered in the bottom of reactor.

In a preferred embodiment of the inventive method, in step (i-1), at first make one or more epoxy alkane A3 of 5wt.% to the 95wt.% amount for the treatment of all to be supplied in the step (i-1)) with H-official's energy precursor compound A1) transform, subsequently with itself and one or more fatty acid esters A2) mix, then will treat all to be supplied to one or more epoxy alkane A3 of 95wt.% to the 5wt.% amount in the step (i-1)) add with the amount of metering, perhaps in step (i-1), at first make one or more epoxy alkane A3 of the 5wt.%-95wt.% amount for the treatment of all to be supplied in the step (i-1)) can precursor compound A1 with H-official) be converted and subsequently with one or more fatty acid esters A2) and one or more epoxy alkane A3 for the treatment of all to be supplied to 95wt.% to the 5wt.% amount in the step (i-1)) add also initiation reaction with the amount of metering.

Epoxy alkane A3), can be regarded as the epoxy alkane (epoxide) with 2-24 carbon atom.They also can step (ii) in as epoxy alkane B1) use.It can be, for example, one or more are selected from following compound: oxyethane, propylene oxide, the 1-butylene oxide ring, 2, the 3-butylene oxide ring, the 2-methyl isophthalic acid, 2-propylene oxide (oxidation iso-butylene), 1-epoxy pentane, 2,3-epoxy pentane, the 2-methyl isophthalic acid, the 2-butylene oxide ring, 3-methyl l-1, the 2-butylene oxide ring, 1-epoxy hexane, 2,3-epoxy hexane, 3,4-epoxy hexane, the 2-methyl isophthalic acid, 2-epoxy pentane, the 4-methyl isophthalic acid, 2-epoxy pentane, 2-ethyl-1, the 2-butylene oxide ring, 1-epoxy heptane, the 1-octylene oxide, 1-epoxy nonane, 1-epoxy decane, 1-epoxy undecane, 1-epoxy dodecane, the 4-methyl isophthalic acid, 2-epoxy pentane, butadiene monoxide, oxidation isopropyl alkene, cyclopentene oxide, cyclohexene oxide, the oxidation suberene, the oxidation cyclooctene, Styrene oxide 98min., oxidation methyl vinylbenzene, the oxidation firpene, monocycle oxidation or how epoxidised fat such as monoglyceride, triglyceride and triglyceride level, epoxidized fatty acid, the C of epoxidized fatty acid ₁-C ₂₄Ester, Epicholorohydrin, Racemic glycidol, and the derivative of Racemic glycidol, for example, methyl glycidyl ether, ethyl ether, 2-ethylhexyl glycidyl ether, glycidyl allyl ether, glycidyl methacrylate, and epoxy functionalized organoalkoxysilane, for example, 3-glycidyl oxygen base propyl trimethoxy silicane, 3-glycidyl oxygen base propyl-triethoxysilicane, 3-glycidyl oxygen base propyl group tripropoxy silane, 3-glycidyl oxygen base propyl group methyl dimethoxysilane, 3-glycidyl oxygen base propyl group ethyl diethoxy silane, 3-glycidyl oxygen base propyl group three isopropoxy silane.

As epoxy alkane A3), preferably use oxyethane and/or propylene oxide, preferred at least 10% oxyethane, and pure oxyethane quite particularly preferably.

If epoxy alkane adds with continuous measurement, the product of then making comprises the polyether chain with block structure.After epoxy alkane is metered into the stage end, then carry out the secondary reaction stage immediately, react away therein remaining epoxy alkane.When the pressure in determining reaction vessel no longer further descends, can reach the end of secondary reaction stage.After the step of reaction, the unreacted epoxide of trace is optionally removed in the vacuum of 1 millibar to 500 millibars absolute pressure.

（i-2）

According to the present invention, in step (i-2), undertaken by adding sulfuric acid from the alkalescence of the thick epoxy alkane adduct of step (i-1), the neutralization at polymerization activity center, sulfuric acid adds by this way so that be included in the purpose of the amount of the catalyzer in the crude polymer in order to neutralize, and makes the 66mol%-100mol% of the employed acid activity that only become in the first catabolic phase.This can by for example use than in and the necessary sulfuric acid as many as of basic catalyst lack 50% sulfuric acid and realize.Because the second catabolic phase of sulfuric acid also has enough pKa, therefore can use in the methods of the invention 0.75mol to 1mol sulfuric acid/mol catalyzer to neutralize, preferred 0.75mol to 0.9mol sulfuric acid/mol catalyzer neutralizes.Although temperature can change in wide in range scope in N-process, but preferably be no more than the highest 100 ℃, preferred 80 ℃, particularly preferably 60 ℃ and 40 ℃ temperature very particularly preferably in N-process, this is because there is hydrolysis susceptibility ester group in the product.

（i-3）

After neutralization had been finished, the water of trace---it is for example introduced by the adding of diluted acid---can be chosen wantonly under the vacuum of 1 millibar to 500 millibars absolute pressure and remove (step (i-3)).In N-process or afterwards, can as required antiaging agent or antioxidant be joined the component A that obtains by this way) in.The salt that forms in N-process is retained in component A) in; That is, do not need other again treatment steps, for example filter.Component A) has at least 70mg KOH/g, preferred 130mg-500mg KOH/g, and the OH value of 180mg-300mg KOH/g particularly preferably.

Step is (ii):

Step in an embodiment of the inventive method (ii) in, with dmc catalyst B2) join the component A that obtains from step (i)) and make itself and one or more epoxy alkane B1) occur to transform until obtain OH value for 3mg to less than component A) OH value, preferably 3mg to 120mg KOH/g, the polyester ether polylol of 14mg to 75mg KOH/g (1) particularly preferably.Before adding dmc catalyst, such as record among the WO 99/14258, also other organic or inorganic acid of a small amount of (1ppm-500ppm) can be joined component A) in.The component A of step in (ii)) with one or more epoxy alkane B1) conversion under dmc catalyst in principle can with preparation process (i) in component A) carry out in the identical reactor.Be positioned at the scope of 10ppm to 1000ppm with respect to the concentration of the dmc catalyst of the amount meter of the finished product (1).

In principle, dmc catalyst B2) by the prior art situation as can be known (referring to, for example, US-A 3,404,109, US-A 3,829,505, US-A 3,941,849 and US-A 5,158,922).For example US-A 5,470,813, among EP-A 700 949, EP-A 743 093, EP-A 761 708, WO 97/40086, WO 98/16310 and the WO 00/47649 dmc catalyst of record in the polymerization of epoxide, have high active and under extremely low catalyst concn (25ppm or still less) can prepare polyether glycol, thereby make the separation of catalyzer from end product usually no longer necessary.Typical example is made of the high reactivity dmc catalyst of describing among the EP-A 700 949, its except double metal cyanide (for example, zinc six cyanogen close cobalt (III)) and organic complex part (for example, the trimethyl carbinol) outside, also comprise number-average molecular weight greater than the polyethers of 500g/mol.

Can also use disclosed alkaline dmc catalyst in EP application number 10163170.3.

The cyanide-free metal-salt that is applicable to prepare the bimetallic cyaniding compounds preferably has general formula (I),

M(X) _n （I）

Wherein

M is selected from following metallic cation: Zn ²⁺, Fe ²⁺, Ni ²⁺, Mn ²⁺, Co ²⁺, Sr ²⁺, Sn ²⁺, Pb ²⁺And Cu ²⁺M is preferably Zn ²⁺, Fe ²⁺, Co ²⁺Or Ni ²⁺,

X be one or more (namely, various) negatively charged ion, be preferably selected from following negatively charged ion: halogen (being fluorine, chlorine, bromine, iodine), oxyhydroxide, sulfate radical, carbonate, cyanate radical, thiocyanate radical, isocyano, isosulfocyanate radical, carboxylate radical, oxalate and nitrate radical;

If X=sulfate radical, carbonate or oxalate, then n be 1 and

If X=halogen, oxyhydroxide, cyanate radical, thiocyanate radical, isocyano, isosulfocyanate radical or nitrate radical, then n is 2,

The cyanide-free metal-salt that perhaps is fit to has general formula (II),

M _r(X) ₃ （II）

Wherein

M is selected from following metallic cation: Fe ³⁺, Al ³⁺And Cr ³⁺,

If X=sulfate radical, carbonate or oxalate, then r be 2 and

If X=halogen, oxyhydroxide, cyanate radical, thiocyanate radical, isocyano, isosulfocyanate radical, carboxylate radical or nitrate radical, then r is 1,

The cyanide-free metal-salt that perhaps is fit to has general formula (III),

M(X) _s （III）

Wherein

M is selected from following metallic cation: Mo ⁴⁺, V ⁴⁺And W ⁴⁺

If X=sulfate radical, carbonate or oxalate, then s be 2 and

If X=halogen, oxyhydroxide, cyanate radical, thiocyanate radical, isocyano, isosulfocyanate radical, carboxylate radical or nitrate radical, then s is 4,

The cyanide-free metal-salt that perhaps is fit to has general formula (IV),

M(X) _t （IV）

Wherein

M is selected from following metallic cation: Mo ⁶⁺And W ⁶⁺

If X=sulfate radical, carbonate or oxalate, then t be 3 and

If X=halogen, oxyhydroxide, cyanate radical, thiocyanate radical, isocyano, isosulfocyanate radical, carboxylate radical or nitrate radical, then t is 6.

The example of the cyanide-free metal-salt that is fit to is zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, Zinc dibenzoate, zinc nitrate, ferrous sulfate (II), ferrous bromide (II), iron protochloride (II), cobalt chloride (II), sulfocyanic acid cobalt (II), nickelous chloride (II) and nickelous nitrate (II).Also can use the mixture of various metal-salts.

The metal cyanide salt that is applicable to prepare the bimetallic cyaniding compounds preferably has logical formula V

(Y) _aM′(CN) _b(A) _c （V）

Wherein

M ' is for being selected from one or more following metallic cations: Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV) and V(V), M ' is preferably and is selected from one or more following metallic cations: Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II)

Y is selected from one or more following metallic cations: basic metal (is Li ⁺, Na ⁺, K ⁺, Rb ⁺, Cs ⁺) and alkaline-earth metal (be Be ²⁺, Ca ²⁺, Mg ²⁺, Sr ²⁺, Ba ²⁺),

A is selected from one or more following negatively charged ion: halogen (being fluorine, chlorine, bromine, iodine), oxyhydroxide, sulfate radical, carbonate, cyanate radical, thiocyanate radical, isocyano, isosulfocyanate radical, carboxylate radical, oxalate and nitrate radical and

A, b and c are integer, and the value of a, b and c is selected by this way so that metal cyanide salt reaches electric neutrality; A is preferably 1,2,3 or 4; B is preferably 4,5 or 6; C is preferably 0.

The example of the metal cyanide salt that is fit to is that potassium six cyanogen close cobalt (III), potassium six cyanogen and close that iron (II), potassium six cyanogen close iron (III), calcium six cyanogen close cobalt (III) and lithium six cyanogen close cobalt (III).

The preferred double metal cyanide that dmc catalyst in the inventive method comprises is for having the compound of general formula (VI)

M _x[M’ _x,(CN) _y] _z （VI）

Wherein M suc as formula definition in (I) to (IV) and

M ' is as defining in the formula V, and

X, x ', y and z are that integer and its are selected by this way so that the bimetallic cyaniding compounds reaches electric neutrality.

Preferably,

X=3, x '=1, y=6 and z=2,

M=Zn(II), Fe(II), Co(II) or Ni(II) and

M '=Co(III), Fe(III), Cr(III) or Ir(III).

The example of the bimetallic cyaniding compounds that is fit to is that zinc six cyanogen close that cobalt (III), zinc six cyanogen close iridium (III), zinc six cyanogen close iron (III) and cobalt (II) six cyanogen close cobalt (III).Other examples of the bimetallic cyaniding compounds that is fit to can be from for example US-A 5,158,922(the 8th hurdle, 29-66 is capable) learn.Particularly preferably, use zinc six cyanogen to close cobalt (III).

The organic complex part that adds is disclosed in for example US-A 5,158 in the process of preparation dmc catalyst, 922(referring to, the 6th hurdle particularly, 9-65 is capable), US-A 3,404,109, US-A 3,829,505, US-A 3,941, and 849, EP-A 700 949, EP-A 761 708, JP-A 4145123, US-A 5,470,813, among EP-A 743 093 and the WO-A 97/40086.---its can with double metal cyanide compound formation complex compound---can be used as the organic complex part for example with the water-soluble organic compounds of heteroatoms (for example oxygen, nitrogen, phosphorus or sulphur).Preferred organic complex part is alcohol, aldehyde, ketone, ether, ester, acid amides, urea, nitrile, sulfide and its mixture.Particularly preferred organic complex part is aliphatic ether (for example glycol dimethyl ether), water-soluble aliphatic series alcohol (for example ethanol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, 2-M3BOL and 2-methyl-3-butyne-2-alcohol), contain the compound (for example, glycol monomethyl tertbutyl ether, glycol monomethyl tertbutyl ether, tripropylene glycol monomethyl ether and 3-methyl-3-oxetane methanol) of aliphatic series or cyclic aliphatic ether group and aliphatic hydroxide radical group.Organic complex part very preferably is selected from one or more following compounds: glycol dimethyl ether, the trimethyl carbinol, 2-M3BOL, 2-methyl-3-alkynes-2-alcohol, glycol monomethyl tertbutyl ether and 3-methyl-3-oxetane methanol.

In the preparation process of dmc catalyst of the present invention, one or more are selected from other complex compound formation component of following compounds optional use: polyethers, polyester, polycarbonate, the polyalkylene glycol sorbitan ester, the polyalkylene glycol glycidyl ester, polyacrylamide, poly-(acrylamide-altogether-vinylformic acid), polyacrylic acid, poly-(vinylformic acid-altogether-toxilic acid), polyacrylonitrile, the vinylformic acid poly alkyl ester, the methacrylic acid poly alkyl ester, polyvinyl methyl ether, the polyvinyl ethyl ether, the acetic acid polyvinyl ester, polyvinyl alcohol, the poly-N-vinyl pyrrolidone, poly-(NVP-altogether-vinylformic acid), polyvinyl methyl ketone, poly-(4-Vinyl phenol), poly-(vinylformic acid-altogether-vinylbenzene) oxazoline polymkeric substance, polyalkyleneimines, toxilic acid and copolymer-maleic anhydride, Natvosol and polyacetal, or glycidyl ether, glycoside, the carboxylicesters of polyhydroxy-alcohol, its bile acide or salt, ester or acid amides, cyclodextrin, phosphorus compound, α, beta-unsaturated carboxylic acid ester or ionic surfactant or interfacial activity compound.

Preferably, in the preparation process of dmc catalyst of the present invention, in the first step, metal-salt (for example, zinc chloride) the aqueous solution is with respect to metal cyanide salt stoichiometry excessive (at least 50mol%) (namely, at least the mol ratio of cyanide-free metal-salt and metal cyanide salt is 2.25 to 1.00) use, and metal cyanide salt (for example, potassium six hydration cobalts) the aqueous solution at the organic complex part (for example, propyl carbinol) transforms under the existence, comprise bimetallic cyaniding compounds (for example, zinc six hydration cobalts) thereby form, water, excessive cyanide-free metal-salt and the suspension of organic complex part.In this case, the organic complex part can be present in the aqueous solution of cyanide-free metal-salt and/or metal cyanide salt, perhaps immediately it is joined in the suspension that obtains after the bimetallic cyaniding compounds is separated out.Confirmed that under vigorous stirring it is favourable that the aqueous solution with cyanide-free metal-salt and metal cyanide salt mixes with the organic complex part.Choose wantonly subsequently and process the suspension that forms in the first step with other complex compounds formation components.In this case, preferably use complex compound to form component in the mixture of water and organic complex part.The preferred method (being the preparation of suspension) that is used for implementing the first step is particularly preferably finished such as the jet-type decollator of describing among WO-A 01/39883 A by using by using mixing nozzle.

In second step, the separation of solid matter (that is, the precursor of catalyzer of the present invention) from suspension is for example centrifugal or filter and to finish by known technology.

In a preferred embodiment modification for the preparation of catalyzer, the solid matter of separation subsequently in the 3rd treatment step with the solution washing of organic complex part (for example, by resuspended and subsequently by filtration or centrifugal Re-isolation).By this way, for example water-soluble by product such as Repone K can be removed from catalyzer of the present invention.Preferably, the amount of the organic complex part in wash water solution is with respect to total solution meter, between 40wt.% to 80wt.%.

In the wash water solution in the 3rd step, the optional adding with respect to total solution meter, preferably other complex compounds of the scope between 0.5wt.% to 5wt.% form component.

In addition, the solid matter that separates of washing is more than once being favourable.For this purpose, for example, can repeat the first washing operation.But preferably with non-aqueous solution, for example organic complex part and other complex compounds form the mixture of component for further washing operation.

Subsequently, be generally under 20 ℃-100 ℃ the temperature and common 0.1 millibar to the pressure of normal pressure (1013 millibars), choose solid matter drying that will separate and optionally washing grinding after wantonly.

Put down in writing among the WO-A 01/80994 by filtration, filter cake washing and the dry preferred method of from suspension, isolating dmc catalyst of the present invention.

The reactions steps of DMC-catalysis (ii) usually can according to step (i) in the component A that under basic catalyst, carries out) the identical treatment principle of preparation carry out.Particularly, use identical epoxy alkane or epoxy alkane mixture; That is the compound A-13 of, listing as epoxy alkane) also can be used as epoxy alkane B1 in (ii) in step).(ii) some of the reactions steps of DMC-catalysis are processed details will be in following discussion.

In one embodiment, component A) mix with dmc catalyst.Preferred a processing in the modification, be heated to 60 ℃-160 ℃, preferred 100 ℃-140 ℃, the utmost point particularly preferably after 120 ℃-140 ℃ the temperature, during preferred 10 minutes to 60 minutes, under agitation sweep the content that blows (strip) reactor with rare gas element.Sweeping with rare gas element in the process of blowing, removing volatiles by the vacuum of in liquid phase, introducing rare gas element and should adding as simultaneously 5 millibars to 500 millibars absolute pressure.The 5wt.%-20wt.% epoxy alkane B1 of the amount meter component A that is being metered into one or more and usually drops in (ii) with respect to step)) after, dmc catalyst is activated.The content that the adding of one or more epoxy alkane can occur in reactor be heated to 60 ℃-160 ℃, preferred 100 ℃-140 ℃, quite particularly preferably before 120 ℃-140 ℃ the temperature, in the process or afterwards; Preferably carry out after blowing sweeping.By the pressure drop of accelerating in the reactor, the activation of catalyzer becomes obviously, and this has also demonstrated the initial conversion of epoxy alkane.Then epoxy alkane or the epoxy alkane mixture of aequum can be supplied in the reaction mixture continuously, temperature of reaction is selected from 20 ℃ to 200 ℃ thus, but preferred 50 ℃ to 160 ℃.In most situation, temperature of reaction is identical with activation temperature.Usually, the activation of catalyzer has carried out so soon so that being metered into of the epoxy alkane that need not to measure separately for the catalyst activation purpose, and randomly at first under the metering rate that reduces, can begin immediately continuous measurement and add one or more epoxy alkane.In addition, in the reactions steps of DMC-catalysis, the temperature of reaction that is metered in the phase process at epoxy alkane can change in described boundary.Equally, in the reactions steps of DMC-catalysis, the mode supplied reactor that one or more epoxy alkane can change: for example by near the floodpipe the reactor bottom that is arranged in the well blend district or current collector, in the measurable adding gas phase or directly add in the liquid phase.For the DMC-catalytic process, preferred modification is to be metered into liquid phase.

Being metered into after the end of epoxy alkane, can follow immediately the secondary reaction stage, wherein the decline of the concentration of unreacted epoxy alkane can come quantitatively by monitor force.After the secondary reaction stage finished, reaction mixture can be for example discharges from a small amount of unconverted epoxy alkane in the vacuum of 1 millibar to 500 millibars absolute pressure or by sweeping to blow randomly quantitatively.As sweeping the result who blows, volatiles, for example (remaining) epoxy alkane vacuum of being applied for simultaneously 5 millibars to 500 millibars absolute pressure by introduce rare gas element or water vapour in liquid phase is removed.Volatiles such as unconverted epoxy alkane remove or in a vacuum or by sweeping to blow and carry out under 20 ℃-200 ℃, preferred 50 ℃-160 ℃ temperature, and preferably under agitation.Sweeping like this blown operation and also can be carried out in so-called stripping tower, and wherein the logistics of rare gas element or water vapour flows towards the direction of product stream.After obtaining constant pressure or by vacuum and/or sweep blow away except volatiles after, product can be discharged from reactor.

The OH value of end product (1) adds up to 3mg KOH/g to less than component A) OH value, preferably 3mg to 120mg KOH/g, particularly preferably 14mg to 75mg KOH/g.

In another embodiment of the inventive method, step (ii) in, will the initiator polyvalent alcohol and dmc catalyst drop in the reactor system and supply continuously component A) together with one or more epoxy alkane B1).Be suitable as step (ii) in the component A for epoxy alkane adduct, part amount of initiator polyvalent alcohol) and/or the previous separately end product of the present invention (1) of preparation; Described epoxy alkane adduct is, for example, polyether glycol, polycarbonate polyol, polyestercarbonate polyvalent alcohol, polyether carbonate polyol, it has the OH value in the scope of 3mg to 1000mg KOH/g for example, preferred 3mg to 300mg KOH/g separately.Preferably, with the component A of part amount) or the end product of the present invention (1) of previous separately preparation as the initiator polyvalent alcohol of step in (ii).Particularly preferably, with the end product of the present invention (1) of previous separately preparation as the initiator polyvalent alcohol of step in (ii).

Preferably, component A) and being metered into simultaneously of one or more epoxy alkane finish, or add component A with the amount of metering at first together) and one or more epoxy alkane B1 of First component), one or more epoxy alkane B1 that adds subsequently the second section amount with the amount of metering), total amount one or more epoxy alkane B1 of the first and second part amounts thus) corresponding to step (ii) in employed one or more epoxy alkane B1) the total amount of amount.Based on step (ii) in altogether the metering one or more epoxy alkane B1) the amount meter, the First component preferably adds up to 60wt.% to 98wt.%, and the second section amount preferably adds up to 40wt.% to 2wt.%.Behind the reagent of adding with the amount of metering, can follow immediately the secondary reaction stage, wherein the consumption of epoxy alkane can come quantitatively by the monitoring to pressure.After obtaining constant pressure, choose wantonly apply aforesaid vacuum for the purpose of removing unconverted epoxy alkane or sweep blow after, discharge end product.

Also can add all component A of amount in (ii) in step) and dmc catalyst and one or more H-officials' energy initial compounds without interruption together with one or more epoxy alkane B1), the molar masss such as described H-official's energy initial compounds especially has, for example, these compounds in 30.0Da to 350Da scope.

' etc. molar mass ' can be regarded as the total mass of the material that contains the Tserevitinov-active hydrogen atom of being divided by the number of Tserevitinov-active hydrogen atom.For the material of hydroxyl group, it is calculated by following formula:

Etc. molar mass=56100/OH value [mg KOH/g]

For example, the OH value can be determined according to the volumetry of DIN53240 instruction, or determine by the NIR spectrography.

In another embodiment of the inventive method, reaction product (1) is discharged from reactor continuously.Under this processing mode, step (ii) in, the dmc catalyst of initiator polyvalent alcohol and part amount is put in the reactor system, and is supplied continuously component A) with one or more epoxy alkane B1) and dmc catalyst, and reaction product (1) is discharged from reactor continuously.Be suitable as the component A for epoxy alkane adduct, part amount of initiator polyvalent alcohol in (ii) in step) and/or the previous separately end product of the present invention (1) of preparation; Described epoxy alkane adduct is, for example has separately polyether glycol, polycarbonate polyol, polyestercarbonate polyvalent alcohol, the polyether carbonate polyol of the OH value in the scope of for example 3mg-1000mg KOH/g, preferred 3mg-300mg KOH/g.Preferably, with the component A of part amount) or the end product of the present invention (1) of previous separately preparation as the initiator polyvalent alcohol of step in (ii).Particularly preferably, with the end product of the present invention (1) of previous separately preparation as the initiator polyvalent alcohol of step in (ii).

In this case, can for example in reactor cascade or tubular reactor, then carry out immediately continuous secondary reaction steps.As mentioned above, volatile constituent can and/or be swept in vacuum and be blown middle removal.

The whole bag of tricks modification in the preparation process of the polyether glycol of processing by the epoxy alkane addition under the effect of DMC-complex compound catalyst is recorded in, for example among WO-A 97/29146 and the WO-A 98/03571.

Preferably, dmc catalyst is retained in the end product, but it also can be by for example isolating with sorbent treatment.The method of separating dmc catalyst is recorded in, and for example US-A 4,987, and 271, among DE-A 31 32 258, EP-A 406 440, US-A 5,391,722, US-A 5,099,075, US-A 4,721,818, US-A 4,877,906 and the EP-A 385 619.

Can be used as by the polyester ether polylol (1) that the inventive method obtains the initial component for the preparation of polyurethane formulations and solid matter or polyurathamc such as polyurethane elastomer, polyurethane flexible foam and hard polyurethane foam.These urethane also can comprise isocyanurate structure unit, allophanate structural unit and biuret structure unit.

Can be similarly theme of the present invention by the urethane that contains polyester ether polylol (1), especially polyurathamc such as polyurethane elastomer, polyurethane flexible foam and the hard polyurethane foam that the inventive method obtains.

These urethane are by the preparation that is converted of following component and organic multiple isocyanate:

I) polyester ether polylol of the present invention (1),

II) randomly, other isocyanate activity compounds,

III) randomly, whipping agent,

IV) randomly, catalyzer,

V) randomly, additive, for example, the hole stablizer.

As other isocyanate activity compounds, component I I), polyether glycol, polyester polyol, polycarbonate polyol, polyether carbonate polyol, polyestercarbonate polyvalent alcohol, polyether carbonate polyol and/or chain propagation agent and/or OH value or NH value for the linking agent of 6mg to 1870mg KOH/g can choose wantonly with as component I in the polyurethane formulations) polyester ether polylol of the present invention (1) mix.

The polyether glycol that is suitable for this for example can be in the presence of as the alkaline hydrated oxide of catalyzer or alkaline alcohol compound and is being added that the anionoid polymerization by epoxy alkane obtains under H-official's energy initial compounds of Tserevitinov-active hydrogen atom of at least a 2-8 of a containing bonding scheme, perhaps by Lewis acid for example antimony pentachloride or boron fluoride etherate in the presence of the cationoid polymerisation of epoxy alkane obtain.The catalyzer that is fit to also has those catalyzer of double metal cyanide (DMC) type, for example be recorded in US-A 3,404,109, US-A 3,829,505, US-A 3,941, and 849, US-A 5,158,922, US-A 5,470, and 813, among EP-A 700 949, EP-A 743 093, EP-A 761 708, WO-A 97/40086, WO-A 98/16310 and the WO-A 00/47649.The epoxy alkane that is fit to and the H-official that some are fit to can have description in the initial compounds part formerly.That replenishes also has as the tetrahydrofuran (THF) of the cyclic ether of Lewis acid polymerization and as the water of starting molecule.Polyether glycol, the preferred rare polyvalent alcohol of polyoxypropylene polyoxy second preferably has the mumber average molar mass of 200Da to 8000Da.Be suitable as the polyether glycol that also has polymer modification of polyether glycol, preferred grafted polyether polyol, those grafted polyether polyols of styrene-based and/or vinyl cyanide particularly, it can pass through vinyl cyanide, vinylbenzene or be 90:10-10:90 by for example weight ratio preferably, the vinylbenzene of preferred 70:30-30:70 and the mixture of vinyl cyanide in position polymerization prepare, aforesaid polyether glycol is fit to, and polyether glycol dispersion, it comprises as disperse phase, usually with 1wt.% to 50wt.%, the mineral filler of the amount of preferred 2wt.% to 25wt.%, polyureas, polyhydrazide, the urethane of the tertiary-amino-containing group of bonding scheme, and/or trimeric cyanamide.

The polyester polyol that is fit to for example can be prepared by the organic dicarboxylic acid with 2-12 carbon atom and polyhydroxy-alcohol, described polyhydroxy-alcohol be preferably have 2-12 carbon atom, the preferred glycol of 2-6 carbon atom.Herein, di-carboxylic acid for example can be considered: succsinic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, decane dicarboxylic acid, dodecanedicarboxylic acid, toxilic acid, fumaric acid, phthalic acid, m-phthalic acid and terephthalic acid.In this case, dicarboxylic acid can use separately the use that also can be mixed with each other.Dicarboxylic acid except free also can use corresponding dicarboxylic acid derivatives, for example has dicarboxylic acid monoesters and/or diester or the dicarboxylic acid anhydride of the alcohol of 1-4 carbon atom.Preferred use is with the mixture, particularly hexanodioic acid of succsinic acid, pentanedioic acid and the hexanodioic acid of the quantitative ratio of for example 20-35/40-60/20-36 weight part.The example of dihydroxyl or polyhydroxy-alcohol is ethylene glycol, Diethylene Glycol, 1,2-and 1, ammediol, dipropylene glycol, methyl isophthalic acid, ammediol, BDO, 1,5-PD, 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol, neopentyl glycol, decamethylene-glycol, 1,12-dodecanediol, glycerine, TriMethylolPropane(TMP) and tetramethylolmethane.Preferred 1，2-ethandiol, Diethylene Glycol, the BDO, 1 of using, the mixture of 6-hexylene glycol, glycerine, TriMethylolPropane(TMP) or at least two kinds of polyhydroxy-alcohols of mentioning, especially the mixture of ethylene glycol, BDO and 1,6-hexylene glycol, glycerine and/or TriMethylolPropane(TMP).Also can use the polyester polyol that is formed by lactone (for example 6-caprolactone) or hydroxycarboxylic acid (for example hydroxycaproic acid and oxyacetic acid).

In order to prepare the purpose of polyester polyol, organic, aromatics or aliphatic polycarboxylic acid and/or polycarboxylic acid derivatives and polyhydroxy-alcohol can be under the modes of catalyst-free or in the presence of the esterifying catalyst, comprising under the atmosphere of the rare gas element of nitrogen, helium or argon gas for example and at 150 ℃-300 ℃ aptly, under the melt of preferred 180 ℃-230 ℃ temperature, randomly under reduced pressure polycondensation is until reach required acid number and OH value.Acid number is advantageously less than 10, preferably less than 2.5.

According to a kind of preferred preparation method, under normal pressure, and subsequently less than 500 millibars, under preferred 1 millibar-150 millibars pressure, under aforementioned temperature, make described esterification mixture polycondensation until acid number is 80-30, preferred 40-30.As esterifying catalyst, can consider for example iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and the tin catalyst of metal, metal oxide or metallic salt form.Yet the polycondensation of aromatics or aliphatic carboxylic acid and polyhydroxy-alcohol can (for example benzene,toluene,xylene or chlorobenzene) be carried out in liquid phase, in the presence of thinner and/or entrainment agent, and purpose is to remove water of condensation by the distillation azeotropic.

In order to obtain the ratio of the required selected di-carboxylic acid of OH value, functionality and viscosity (derivative) Yu polyhydroxy-alcohol, and the functionality of selected alcohol can be determined in simple mode by those skilled in the art.

The polycarbonate polyol that is fit to is those known type itself, it can be for example by glycol (for example, 1,2-propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, Diethylene Glycol, triethylene glycol, TEG, low polytetramethylene glycol and/or oligomeric hexamethylene glycol) with the preparation that is converted of diaryl carbonate and/or dialkyl carbonate (for example, diaryl carbonate, methylcarbonate and α-ω-bischloroformate or phosgene).

The polyether carbonate polyol that is fit to for example can obtain by carbonic acid gas and epoxy alkane in copolymerization on the initial compounds of polyfunctional hydroxyl group.Being used for this catalyzer that is fit to, especially is above-mentioned DMC type catalyzer.

The linking agent of dual functional chain propagation agent and/or preferred trifunctional or four senses can mix with the polyester ether polylol (1) that uses for the purpose of the mechanical property that changes urethane (especially hardness) according to the present invention.The chain propagation agent (for example alkane glycol, two aklylene glycols and polyalkylene polyvalent alcohol) that is fit to and linking agent (for example, the oligomeric polyalkylene polyvalent alcohol that trihydroxy-or tetrahydroxy alcohol ethyl have the functionality of 3-4) usually has less than 800Da preferred 18Da-400Da and the molecular weight that is in particular 60Da-300Da.Preferably as chain propagation agent use for having the alkane glycol of 2-12 carbon atom, for example ethylene glycol, 1,3-PD, 1,5-PD, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, 1, the 10-decanediol and, be in particular BDO and the dioxane glycol with 4-8 carbon atom, for example Diethylene Glycol and dipropylene glycol and polyoxyalkylene diols.Having of also being fit to has side chain and/or the undersaturated alkane glycol that is no more than 12 carbon atoms usually, for example, 1, the 2-propylene glycol, the 2-methyl isophthalic acid, ammediol, the 3-methyl isophthalic acid, the 5-pentanediol, 2,2-dimethyl-1, ammediol, 2-butyl-2-ethyl-1,3-PD, 2-butylene-Isosorbide-5-Nitrae-two pure and mild 2-butyne-1, the 4-glycol, terephthalic acid and the diester with glycol of 2-4 carbon atom, for example, terephthalic acid two (glycol ester) or terephthalic acid two (BDO ester), and the hydroxy alkylidene ester of quinhydrones or Resorcinol, for example Isosorbide-5-Nitrae-two (beta-hydroxyethyl) quinhydrones or 1,3-(beta-hydroxyethyl) Resorcinol.Also can use the alkanolamine with 2-12 carbon atom, thanomin for example, 2-aminopropanol and 3-amino-2,2-dimethyl propyl alcohol, N-alkyl dioxane hydramine, for example N-methyl and N-ethyldiethanolamine, (ring) aliphatic diamine with 2-15 carbon atom, for example 1, the 2-ethylene diamine, 1, the 3-trimethylene diamine, 1,4-butylene diamine and 1, the 6-hexamethylene-diamine, isophorone diamine, 1,4-hexamethylene diamines and 4,4 '-diamino-dicyclohexyl methane, the N-moieties has 1-20, the N-alkyl of preferred 1-4 carbon atom replaces, N, N '-dialkyl group that replace with diamines (it also can be replaced by alkyl on aromatic moieties) aromatics, for example, N, N '-diethyl diamines, N, N '-two-secondary pentamethylene diamine, N, N '-two-secondary hexanediamine, N, N '-two-secondary decamethylene diamine and N, N '-dicyclohexyl diamines, ortho-, meta-or p-or meta-phenylenediamine, N, N '-dimethyl-, N, N '-diethyl-, N, N '-di-isopropyl-, N, N '-two-second month in a season-butyl-, N, N '-dicyclohexyl-4,4 '-diaminodiphenyl-methane, N, N '-two-second month in a season-butyl biphenyl amine, methylene radical-two (4-amino-3-methyl benzoate), 2,4-chloro-4,4 '-diaminodiphenyl-methane, 2,4-and 2,6-tolylene diamine.The linking agent that is fit to is for example glycerine, TriMethylolPropane(TMP) or tetramethylolmethane.

Also can use different chain propagation agents and linking agent mixture each other and the mixture of chain propagation agent and linking agent.

The organic multiple isocyanate that is fit to is cyclic aliphatic, araliphatic, aromatics and heterocycle polyisocyanates, for example is recorded in W.Siefken in Justus Liebigs Annalen der Chemie, 562, the 75-136 pages or leaves, and for example formula is Q (NCO) _nThese, n=2-4 wherein, be preferably 2, and Q represents to have 2-18, the aliphatic hydrocrbon residue of preferred 6-10 carbon atom, has 4-15, the cycloaliphatic hydrocarbon residue of preferred 5-10 carbon atom, has 6-15, the aromatic hydrocarbon residue of preferred 6-13 carbon atom or have 8-15, preferably the araliphatic hydrocarbon residue of 8-13 carbon atom.What be fit to has, two isocyanic acid ethyls for example, two isocyanic acids 1,4-four methylene esters, two isocyanic acids 1,6-six methylene esters (HDI), two isocyanic acids 1, the 12-dodecyl ester, tetramethylene-1, the 3-vulcabond, hexanaphthene-1,3-and-1, the any mixture of 4-vulcabond and these isomer, 1-isocyanato-3,3, the 5-trimethylammonium-(DE-B 1 202 785 for 5-isocyanic acid methylcyclohexane, US-A 3,401,190), 2,4-and 2, the arbitrarily mixture of 6-hexahydrotoluene vulcabond and these isomer, six hydrogen-1,3-and six hydrogen-1, the 4-phenylene vulcabond, cross hydrogen-2,4 '-and-4,4 '-diphenylmethanediisocyanate, 1,3-and Isosorbide-5-Nitrae-phenylene vulcabond (DE-A19627907), Isosorbide-5-Nitrae-durol vulcabond (DDI), 4,4 '-stibene vulcabond (DE-A 196 28 145), 3,3 '-dimethyl-4,4 '-diphenylene vulcabond (DIBDI) (DE-A 195 09 819), 2,4-and 2, the any mixture of 6-tolylene diisocyanate (TDI) and these isomer, ditan-2,4 '-vulcabond and/or ditan-4,4 '-vulcabond (MDI) or naphthalene-1,5-vulcabond (NDI).

In addition; can consider according to the present invention; for example: triphenyl methane-4; 4 '; 4 " triisocyanate; polyphenylene polymethylene polyisocyanates can obtain by the condensation of for example aniline-formaldehyde and phosgenation subsequently; and for example be recorded among the GB-A 874 430 and GB-A 848 671; according to US-A 3; 454; between 606 and to isocyanato phenyl sulfonyl isocyanic ester; for example be recorded in US-A 3; 277; perchloro aryl polyisocyanates in 138; for example be recorded in US-A 3; 152; 162 and DE-A 25 04 400; the polyisocyanates with carbodiimide group among DE-A 25 37 685 and the DE-A 25 52 350; according to US-A 3; 492; 301 norbornene alkyl diisocyanate; for example be recorded in GB-A 994 890; the polyisocyanates with allophanate groups among BE-B 761626 and the NL-A 7102524; for example be recorded in DE-C 1 022 789; the polyisocyanates with isocyanurate group among DE-C 1 222 067 and DE-C 1 027 394 and DE-A 1 929 034 and the DE-A 2 004 048; for example be recorded in BE-B 752261 or US-A 3; 394; 164 and US-A 3; 644; the polyisocyanates with polyurethanyl group in 457; the polyisocyanates with acylated urea group according to DE-C 1 230 778; for example be recorded in US-A 3; 124; 605; US-A 3; 201; 372 and US-A 3; 124; 605 and GB-B 889 050 in the polyisocyanates with biuret group; be recorded in US-A 3; 654; passing through in 106 telomerizes the polyisocyanates of (telomerisation) reaction preparation; for example at GB-B 965 474 and GB-B 1 072 956 and the polyisocyanates with ester group that in DE-C 1 231 688, indicates; according to the aforementioned isocyanic ester of DE-C 1 072 385 and the converted product of acetal; and according to US-A 3; 455,883 the polyisocyanates that contains polymeric aliphatic ester.

Also can use the distillation leftover with isocyanate groups of optional dissolved in one or more aforementioned polyisocyanates that in the technology production process of isocyanic ester, generates.In addition, also can use any mixture of aforementioned polyisocyanates.

The polyisocyanates that easily obtains on the preferred operation technique, for example 2,4-and 2, the any mixture of 6-tolylene diisocyanate and these isomer (' TDI '), polyphenylene polymethylene polyisocyanates can prepare by for example aniline-formaldehyde condensation and phosgenation subsequently (' thick MDI '), and has a carbodiimide group, polyurethanyl group, allophanate groups, isocyanuric acid ester, the polyisocyanates of urea groups or biuret group (' modified polyisocyanate '), especially derived from 2,4-and/or 2,6-tolylene diisocyanate or 4,4 '-and/or 2,4 '-those modified polyisocyanates of diphenylmethanediisocyanate.Naphthalene-1, the mixture of 5-vulcabond and the polyisocyanates mentioned is also very suitable.

Also can be used the prepolymer with isocyanate groups, it can obtain by following method: the isocyanate-reactive components (as mentioned above) of the polyester ether polylol that the present invention of part amount or total amount uses and/or part amount or total amount, optional polyester ether polylol and at least a TDI, MDI, DIBDI, NDI, the DDI of being selected from that uses with the present invention, preferred 4,4 '-MDI and/or 2,4-TDI and/or 1, the aromatic diisocyanate of 5-NDI or polyisocyanates mix to transform, and have the polyaddition products of polyurethanyl group and isocyanate groups with formation.This polyaddition products has the NCO content of 0.05wt.% to 40.0wt.%.According to a preferred embodiment of using, the prepolymer that contains isocyanate groups only passes through polymer polyol---namely, polyester ether polylol used according to the invention and/or polyether glycol, polyester polyol or polycarbonate polyol---with polyisocyanates (preferred 4,4 '-MDI, 2,4-TDI and/or 1, the preparation that is converted 5-NDI).

Prepolymer with isocyanate groups can prepare in the presence of catalyzer.Yet, also can under catalyst-free, prepare and have the prepolymer of isocyanate groups and also can be for the purpose for preparing urethane in reaction mixture, add these prepolymers.

As optional whipping agent---the component III of using), can make water, itself and organic multiple isocyanate or the prepolymer with isocyanate groups react in position, form carbonic acid gas and amino group, amino group transfers further to react to form urea groups with other isocyanate groups and it plays chain extension agent in this case.If add entry in order to set required density in polyurethane formulations, then the normally used water yield is with respect to component I), IV) and weight V) count 0.001wt.% to 6.0wt.%.

Gas or evaporation and under normal pressure, have-40 ℃ to 120 ℃ under the impact of the polyaddition reaction of heat release, the combination of the volatile inorganic or organic substance of the favourable boiling point in preferred 10 ℃ to the 90 ℃ scopes also can replace water, or preferred mixing with water and be used as pneumatogen.As organic blowing agent, for example have, the alkane that acetone, ethyl acetate, methyl acetate, halogen replace, for example methylene dichloride, chloroform, ethylene dichloride, vinylidene chloride, single fluoro trichloromethane, chlorodifluoromethane, Refrigerant 12, HCFCs is R 134a, R 245fa and R 365mfc for example, also can use unsubstituted alkane for example butane, Skellysolve A, iso-pentane, pentamethylene, hexane, heptane or ether.As inorganic foaming agent, can consider air, CO ₂Or N ₂O.Foaming effect also can obtain by being added under the temperature that is higher than room temperature the compound that decomposes and be accompanied by such as the elimination of nitrogen and/or carbon dioxide, azo-compound for example, for example Cellmic C 121 or azo isopropylformic acid nitrile, or the salt of azo-compound, the for example ammonium salt of bicarbonate of ammonia, ammonium carbamate or organic carboxyl acid, for example mono-ammonium of propanedioic acid, boric acid, formic acid or acetic acid.The principle that the details of the use of the example of other whipping agents, relevant whipping agent and whipping agent are selected is recorded in R.Vieweg, A.

(editor): ' Kunststoff-Handbuch ', VII volume, Carl-Hanser-Verlag, Munich1966,108f, 453ff and 507-510 page or leaf and at D.Randall, S.Lee(edits): ' The Polyurethanes Book ', John Wiley﹠amp; Sons, Ltd., London2002 is in the 127-136 page or leaf, 233 pages and the 261st page of the 232nd –.

The amount of suitable solid blowing agent, low-boiling point liquid or the gas that adopts (it can use separately or separately with mixture, for example uses as liquid form mixt or gaseous mixture or as the form of gaseous state-liquid form mixt) depends on the density of the urethane of pursuing and the quantity of employed water.Aequum can easily be determined from experience.Gratifying result is generally 0.5 weight part to 35 weight part, the solid matter of the amount of preferred 2 weight part to 15 weight parts, 1 weight part to 30 weight part, the liquid of the amount of preferred 3 weight part to 18 weight parts and/or 0.01 weight part to 80 weight part, the gas of the amount of preferred 10 weight part to 35 weight parts is separately with respect to component I), II) and the weighing scale of polyisocyanates.For example, with the gas of air, carbonic acid gas, nitrogen and/or helium load or can be by recipe ingredient I), II), IV) and V) carry out and/or undertaken by polyisocyanates.

As component I V, the amine catalyst that can use those skilled in the art to be familiar with, tertiary amine for example, such as triethylamine, Tributylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ', N '-tetramethylethylened, five methyl diethylentriamine and higher homologue (DE-OS 26 24 527 and DE-OS 26 24 528), 1,4-diazabicyclo (2,2,2) octane, N-methyl-N '-dimethylaminoethyl piperazine, two (dimethylamino alkyl) piperazine (DE A 26 36 787), N, the N-dimethyl benzylamine, N, N-dimethyl cyclohexane base amine, N, the N-diethyl benzylamine, two (N, the N-diethyl aminoethyl) hexanodioic acid, N, N, N ', N '-tetramethyl--1, the 3-butanediamine, N, N-dimethyl-β-phenyl-ethylamine, two (dimethyl aminopropyl) urea, 1, the 2-methylimidazole, glyoxal ethyline, monocycle and dicyclo amidine (DE-A 1 720 633), two (dialkyl amido) alkyl oxide (US-A 3,330, and 782, DE-B 1 030 558, DE-A 1 804 361 and DE-A 26 18 280) and tertiary amine (according to DE-A 25 23 633 and DE-A 27 32 292) with amide group (preferred carbonylamino group).As catalyzer, can consider the known Mannich base that is formed by secondary amine (for example dimethyl amine) and aldehyde (preferred formaldehyde) or ketone (for example acetone, methylethylketone or pimelinketone) and phenols (for example phenol or alkyl replace phenol).As having of catalyzer the respond tertiary amine of active hydrogen atom of isocyanate groups is had, for example trolamine, tri-isopropanolamine, N methyldiethanol amine, N-ethyldiethanolamine, N, N-dimethylethanolamine and and epoxy alkane, for example converted product of propylene oxide and/or oxyethane and according to the second month in a season/tertiary amine of DE A 27 32 292.As catalyzer, also can use the silicon amine with carbon-silicon key, for example be recorded in US-A 3,620, in 984, for example 2,2,4-trimethylammonium-2-sila morpholine (morpholiine) and 1,3-diethylamino methyl tetramethyl disiloxane.In addition, also can consider nitrogenous base, for example tetraalkylammonium hydroxides also has Hexahydrotriazine.Reaction between NCO group and the Tserevitinov active hydrogen atom also can be accelerated widely by lactan and azepine lactan, thus at first at lactan with have between the compound of acidic hydrogen and form complex compound.

In addition; as the catalyzer (component I V) that is used for the object of the invention; also can use common organometallic compound; preferably have for example tin of organic carboxyl acid (II) salt of machine tin compound; the for example dialkyl tin (IV) of tin acetate (II), stannous octoate (II), thylhexoic acid tin (II) and taurine tin (II) and mineral acid and organic carboxyl acid, for example dibutyltin diacetate, dibutyl tin laurate, toxilic acid dibutyl tin, oxalic acid dioctyl tin and dichloride dibutyl tin.Except these, sulfocompound for example two-n-octyl tin thiolate (US-A 3,645,927) also can be used.

With the catalyzer of ad hoc fashion catalyzing N CO group trimerization for the preparation of the polyurethane material purpose with a high proportion of what is called many (isocyanic ester) structure (' PIR foam ').Usually, for the OH group the significantly excessive prescription of NCO group for the preparation of these materials.Usually the PIR foam of making has the index of 180-450, and the ratio that described index is defined as isocyanate groups and oh group multiply by the factor 100.The catalyzer that helps the isocyanic ester structure representation is metal-salt, for example potassium acetate or sodium acetate, Sodium octoate and aminocompound, for example 1,3,5-three (3-dimethyl aminopropyl) Hexahydrotriazine.

Usually, catalyzer or catalyst combination be with approximately between 0.001wt.% and the 10wt.%, particularly the amount of 0.01wt.% to 4wt.% is used, with respect to having at least two to the respond total amount meter of compound of active hydrogen atom of isocyanic ester.

Under the whipping agent that lacks moisture and physics or chemical action, also can prepare compact-type urethane, for example polyurethane elastomer or urethane cast elastomers.

In the process of preparation compact-type or polyurathamc, can choose wantonly and use simultaneously additive---component V).The surfactant additive that can mention has, for example emulsifying agent, foaming stabiliser, pore regulator, fire retardant, nucleator, antioxygen, stablizer, lubricant and releasing agent, dyestuff, dispersing auxiliary and pigment.As emulsifying agent, for example can consider, the salt of the sodium salt of Viscotrol C sulfonate or lipid acid and amine is oleic acid diethylamine or stearic acid diethanolamine for example.Basic salt or the ammonium salt of sulfonic acid (for example dodecylbenzene sulfonic acid or dinaphthyl methane-disulfonic acid), or the basic salt of lipid acid (for example ricinolic acid) or polymerized fatty acid or ammonium salt also can be used as surfactant additive simultaneously.As foaming stabiliser, at first consider polyether silicone.These compounds are usually synthetic in such a way: the multipolymer that is connected with propylene oxide by oxyethane is connected with polydimethylsiloxaneresidue residue.Like this foaming stabiliser of type rely on terminal OH group esterification or can be to respond activity or to the reactionless activity of isocyanic ester of isocyanic ester.They for example are recorded among US-A 2,834,748, the US-A 2,917,480 and US-A 3,629,308.Edit at G.Oertel(): ' Kunststoff-Handbuch ', VII volume, Carl-Hanser-Verlag, Munich can reproduce the general structure of this foaming stabiliser among the Vienna1993,115 pages of the 113rd –.Usually interested especially is by according to the polysiloxane of the allophanate groups branching of DE-A 25 58 523-polyalkylene oxide hydrocarbon copolymer.In addition other organopolysiloxanes, oxyethylation induced by alkyl hydroxybenzene, oxyethylation Fatty Alcohol(C12-C14 and C12-C18) and the paraffin oil that is fit to and pore regulator be paraffin, Fatty Alcohol(C12-C14 and C12-C18) and dimethyl polysiloxane for example.In addition, have as the oligomeric polyacrylic ester of the polyalkylene oxide hydrocarbon residue of side group and fluothane residue and be fit to improve the dispersion, pore structure of emulsifying effect, filler and/or it is stable.Surfactant is usually in the component I with respect to 100 weight parts) the amount of 0.01 weight part-5 weight part use.Also can add reaction suppressor; acid-respons material hydrochloric acid for example for example; or organic acid and acyl halide; and known pigment or dyestuff and flame-proofing agent; for example three (chloroethyl) phosphoric acid salt, three cresyl phosphoric acid salt or ammonium phosphate and polyphosphate also have stablizer, softening agent and fungicidal and the germicidal action material of resisting aging and weathering.Randomly follow surfactant additive, foaming stabiliser and pore regulator, reaction suppressor, stablizer, fire retardant material, softening agent, dyestuff and the filler of use and antifungal according to the present invention and press down bacterium reactive materials other examples and be recorded in R.Vieweg, A. about the use pattern of these additives and the details of binding mode

(editor): ' Kunststoff-Handbuch ', the VII volume, Carl-Hanser-Verlag, Munich1966 is in the 103-113 page or leaf.

In order to prepare the purpose of urethane, the isocyanate groups in the polyisocyanates and component I), II), III), IV) and V) in can greatly change the respond quantity ratio of active hydrogen atom of isocyanic ester.Usually, this ratio is 0.7:1-5:1, corresponding to the index of 70-500.

In order to prepare the purpose of polyether ester of the present invention, by known single stage method, prepolymer method or the method initiation reaction component of half prepolymer method and the conversion of polyisocyanates, the preferred mechanical means of using for example is recorded among the US PS 2,764,565.The details about processing unit (plant) that also can consider according to the present invention be recorded in Vieweg and

(editor): Kunststoff-Handbuch, the VII volume, Carl-Hanser-Verlag, Munich1966 is in the 121-205 page or leaf.

In the process of preparation foam, according to the present invention, foaming also can be carried out in the mould of sealing.In this case, reaction mixture is introduced in the mould.As moulding stock, can consider metal (for example aluminium), or plastics (for example Resins, epoxy).In mould, the reaction mixture of foaming expands and forms moulded parts.In this case, the mould foaming can be carried out by this way so that the surface of molded parts has vesicular structure.Molded parts has closely knit surface and porous core but the mode that it can also be such is carried out.In the context herein, method can also be so so that so many foamed reaction mixture introduce in the mould so that formed foam fills up mould just.But operation can also such mode be carried out so that introduce in the mould than fill up the more foamed reaction mixture of the necessary foamed reaction mixture of mould inside with foam.In the situation about in the end indicating, therefore, operation (overcharging) is carried out with so-called ' cross filling ', the such tupe of type, and for example by US PS 3,178,490 and US PS 3,182,104 is known.

In the process of mould foaming, usually use the releasing agent of above having mentioned.They are known ' external release agent ', for example silicone oil on the one hand; And on the other hand, also can use the mixture of so-called ' internal mold release ', optional and external release agent, as be found in for example DE-OS 2 121 670 and DE-OS 2 307 589.

But foam also can prepare by block foaming or by known double conveyor technique (referring to ' Kunststoffhandbuch ', VII volume, Carl Hanser Verlag, Munich, Vienna, 1993 the 3rd editions, the 148th page) certainly.

Foam can or prepare in mould by the whole bag of tricks of block foam manufacturing.In the process of foam block preparation, in preferred embodiment of the present invention, except polyether glycol of the present invention, also use those to have at least 50wt.%, preferably the polyether glycol of 60wt.% propylene oxide (PO) ratio at least.Be the purpose of preparation cold-curing moulded foam, especially have greater than 40mol%, the polyether glycol greater than the uncle OH group ratio of 50mol% has proved valuable especially.

Embodiment

The raw material that uses:

Soya-bean oil:

Soya-bean oil (refining, namely through going Yelkin TTS, neutralization, decolouring and steam stripped), Sigma-Aldrich Chemie GmbH, Munich, DE

1076: octadecyl-3-(3,5-, two-tertiary butyl-4-hydroxy benzene) propionic ester, Ciba Specialty Chemicals(is BASF now)

Step (i) preparation component A-1 according to the inventive method:

Step (i-1):

Use Sorbitol Powder (as the solution in the water) as component A1)

Use soya-bean oil as component A2)

Use propylene oxide and oxyethane as component A3)

The aqueous solution of 944.8g70% Sorbitol Powder is injected the 10L autoclave with the 2.33g KOH aqueous solution (KOH that contains 44.9wt.%).Under agitation (450rpm, trellis agitator) dewaters in a vacuum until obtain 150 ℃ temperature under less than 10 millibars absolute pressure.Then under 100 millibars-120 millibars absolute pressure by passing into the 50ml nitrogen/minute content of reactor is swept and to be blown 2 hours.Under 150 ℃, in 3.43 hours, be metered into the 1452.7g propylene oxide; In this case, obtain the absolute total pressure of 2.45 bar.After 1.37 hours, be cooled to room temperature at 150 ℃ of lower secondary reactions, add 3125.6g soya-bean oil by uncapping of reactor.By with nitrogen three extraordinarily straightening to 3 bar absolute pressure and remove oxygen in the reactor by being decompressed to subsequently normal atmosphere.After being heated to 150 ℃, the absolute pressure of 2.8 bar is set with nitrogen, then in 2.9 hours, the stirring velocity of 726.4g oxyethane with 450rpm is metered into.After secondary reaction 7 hours, be cooled to 80 ℃.

Step (i-2):

Follow immediately step (i-1), at 80 ℃ of lower sulfuric acid that add 13.64g12.12%, then stirred 1 hour.

Step (i-3):

And then step (i-2) is adding 3.011g

After 1076, under 1 millibar absolute pressure, 110 ℃, dewatered 3 hours.Obtain the intermediate product (component A-1) of clarification, its OH value is that 195mg KOH/g, the viscosity under 25 ℃ are that 388mPas and acid number are 216ppm KOH.

The step of the method according to this invention (i) preparation component A-2:

Step (i-1):

Use Sorbitol Powder (as the solution in water) as component A1)

Use soya-bean oil as component A2)

Use oxyethane as component A3)

The aqueous solution of 974.3g70% Sorbitol Powder is injected the 10L autoclave with the 2.18g KOH aqueous solution (KOH that contains 44.82wt.%).Under agitation (450rpm, trellis agitator) dewatering 3 hours under 110 ℃, under the vacuum of 10 millibars absolute pressures.Then under 100 millibars to 120 millibars absolute pressure by passing into the 100ml nitrogen/minute content of reactor is swept and to be blown 2 hours.Under 110 ℃, add 3296.0g soya-bean oil by uncapping of reactor.By with nitrogen three extraordinarily straightening to 3 bar absolute pressure and remove oxygen in the reactor by being decompressed to subsequently normal atmosphere.Be heated to after 130 ℃ of the temperature, the absolute pressure of 2.5 bar is set with nitrogen, then in 6.09 hours, the stirring velocity of 2021.5g oxyethane with 450rpm is metered into.After 5.82 hours, be cooled to 42 ℃ at secondary reaction.

Step (i-2):

And then step (i-1) at 42 ℃ of lower sulfuric acid that add 12.95g11.89%, then stirred 1 hour.

Step (i-3):

And then step (i-2) is adding 2.904g After 1076, under 1 millibar absolute pressure, 110 ℃, dewatered 3 hours.Obtain the intermediate product (component A-2) of clarification, its OH value is that the viscosity under the 203mg KOH/g, 25 ℃ is that 486mPas and acid number are 170ppm KOH.

Embodiment 1---according to the conversion of present method step component A-1 (ii)

Use propylene oxide and oxyethane as B component 1)

Use dmc catalyst as B component 2) (according to embodiment 6 preparations of WO-A 01/80994)

In the reactor of a 1L, drop into 150g component A-1 and 0.025g B component 2) then under agitation be heated to 130 ℃.Under this temperature, under the absolute pressure of＜0.1 bar, blew 30 minutes by nitrogen sweep.Subsequently, under agitation, be metered in this reactor at the mixture of 130 ℃ of lower altogether 314g propylene oxide and 35g oxyethane.For the purpose of deactivated catalyst, at first only this mixture metering ground of 22g is added then metering and interrupt.After 30 minutes, descend to indicate the initial activation of catalyzer at original measurement by the acceleration of pressure in the reactor, so that the epoxide of residual content can be without interruption in 60 minutes.Until after the constant pressure, be cooled to 90 ℃ and under the vacuum of 10 millibars absolute pressure, volatile part was removed subsequently secondary reaction 180 minutes in 30 minutes.

The product that obtains has the OH value of 57.5mg KOH/g and the viscosity of 568mPas.

Embodiment 2---according to the conversion of present method step component A-1 (ii)

Use propylene oxide and oxyethane as B component 1)

In the reactor of a 1L, drop into 150g component A-1 and 0.015g dmc catalyst (according to embodiment 6 preparations of WO-A 01/80994), then under agitation be heated to 130 ℃.Under this temperature, under the absolute pressure of＜0.1 bar, blew 30 minutes by nitrogen sweep.Subsequently, under agitation, be metered in this reactor at the mixture of the lower altogether 314g propylene oxide of 130 ℃ of temperature and 35g oxyethane.For the purpose of deactivated catalyst, at first only this mixture metering ground of 22g is added then metering and interrupt.After 30 minutes, descend to indicate the initial activation of catalyzer at original measurement by the acceleration of pressure in the reactor, so that the epoxide of residual content can be without interruption in 60 minutes.Until after the constant pressure, be cooled to 90 ℃ and under the vacuum of 10 millibars absolute pressure, volatile part was removed subsequently secondary reaction 180 minutes in 30 minutes.

The product that obtains has the OH value of 58.0mg KOH/g and the viscosity of 541mPas.

Embodiment 3-is according to the conversion of present method step component A-2 (ii)

Use propylene oxide and oxyethane as B component 1)

In the reactor of a 1L, drop into 150g component A-2 and 0.029g dmc catalyst (according to embodiment 6 preparations of WO-A 01/80994), then under agitation be heated to 130 ℃.Under this temperature, under the absolute pressure of＜0.1 bar, blew 30 minutes by nitrogen sweep.Subsequently, under agitation, be metered in this reactor at the mixture of the lower altogether 383g propylene oxide of 130 ℃ of temperature and 43g oxyethane.For the purpose of deactivated catalyst, at first only this mixture metering ground of 25g is added then metering and interrupt.After 30 minutes, descend to indicate the initial activation of catalyzer at original measurement by the acceleration of pressure in the reactor, so that the epoxide of residual content can be without interruption in 60 minutes.Until after the constant pressure, be cooled to 90 ℃ and under the vacuum of 10 millibars absolute pressure, volatile part was removed subsequently secondary reaction 180 minutes in 30 minutes.

The product that obtains has the OH value of 52.2mg KOH/g and the viscosity of 716mPas.

The preparation of component A-3 (alkoxide of polymerization)

(contrast)

Aqueous sorbitol solution and the 55.33g KOH aqueous solution (KOH that contains 45.00wt.%) of 811.7g70% are injected the 10L autoclave together.Under agitation (450rpm, trellis agitator) dewatered under 125 ℃ temperature 3 hours in a vacuum.Then under 100 millibars to 120 millibars absolute pressure by passing into the 50ml nitrogen/minute content of reactor is swept and to be blown 2 hours.After being cooled to 107 ℃, in 13.53 hours, the stirring velocity metering ground of 5431.8g propylene oxide with 450rpm is added.After 3.43 hours, be cooled to 80 ℃ at secondary reaction.Under this temperature, add the KOH solution of 306.7g45.00wt.%.Then, in the vacuum of 10 millibars absolute pressures, in 3 hours, in 125 ℃ of lower (450rpm) desolventizing water and reaction water of stirring of temperature.Then, under this temperature, under 100 millibars to 120 millibars absolute pressure, by passing into the 50ml nitrogen/minute content of reactor is swept and to be blown 2 hours, obtain the alkoxide A-3 of polymerization.

Embodiment 4(contrast): the conversion according to the component A-3 of present method step (i), without excessively neutralization, filtration is arranged, Separation-free is (ii)

Use the alkoxide A-3 of polymerization as component A1)

Use soya-bean oil as component A2)

Use propylene oxide as component A3) and B2)

Use KOH as B component 1)

The alkoxide A-3 of 1601.9g polymerization is injected the 10L autoclave.Under agitation (450rpm, trellis agitator), by with nitrogen three extraordinarily straightening to 3 bar absolute pressure and remove oxygen residual in the reactor by being decompressed to subsequently 10 millibars.After being heated to 110 ℃, in 0.5 hour, the stirring velocity metering ground of 80.1g propylene oxide with 450rpm is added.After secondary reaction 2 hours, be cooled to 45 ℃.Under this temperature, add 741.2g soya-bean oil by uncapping of reactor.Then, by with nitrogen three extraordinarily straightening to 3 bar absolute pressure and remove oxygen residual in the reactor by being decompressed to subsequently 10 millibars.After being heated to 105 ℃, in 5.28 hours, 3603.5g propylene oxide metering ground is added in the autoclave.After 7.63 hours, be cooled to 40 ℃ at secondary reaction, then add the sulfuric acid of 913.1g4.08% and stirred 1 hour.Then, approximately under 15 millibars except anhydrating, simultaneously temperature is increased to 80 ℃ from 40 ℃.The salt of separating out is by bed filter (T750) filtering.Adding 2.972g After 1076, under 1 millibar, thoroughly heated 3 hours in 110 ℃.This is 51.2mg KOH/g with reference to the OH value that product presents, and 25 ℃ viscosity is that 593mPas and acid number are 760ppm KOH.

Foaming embodiment

The starting material that use:

Component III): water

Component I V):

Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane (33wt.%) in the IV.1 dipropylene glycol (67wt.%) 33LV, Air Products, Hamburg, Germany).

Two (dimethylamino diethyl) ethers (70wt.%) in the IV.2 dipropylene glycol (30wt.%) A1, Momentive Performance Materials, Germany).

The tin of IV.32-thylhexoic acid (II) salt (

SO, Rheinchemie, Mannheim, Germany).

Component V):

V.1 polyethers-siloxanes suds-stabilizing agent

BF2370(Evonik Goldschmidt GmbH, Germany).

Isocyanate component T80: the mixture and its NCO content with 48wt.% that are consisted of with the weight ratio of 80:20 by 2,4-TDI and 2,6-TDI.

The preparation of the polyurethane flexible block foam among embodiment 5 – 7

Under the common process condition for the preparation of the polyurethane flexible block foam, in a step process, foam to process initial component by bulk.The amount of the index (according to this table, producing the amount of employed polyisocyanate component with respect to component I) of technique has been described in detail in detail) in the table 1.Index (isocyanate index) is specially amount and the stoichiometry of the isocyanic ester (NCO) of actual use, the amount of the isocyanic ester (NCO) that namely calculates, per-cent:

Index=[(amount of the isocyanic ester of use): (amount of the isocyanic ester of calculating)] * 100

The weight of every volume is measured according to DIN EN ISO845.

Compressive strength under the distortion of period 4 40% (CLD40%) has been measured since according to DIN EN ISO 3386-1-98.

Tensile strength and elongation at break are measured according to DIN EN ISO 1798.

Compression set (CS90%) under 90% distortion is measured according to DIN EN ISO 1856-2000.

Table 1: polyurethane flexible block foam; Prescription and performance

		5	6	The 7(contrast)
					The polyvalent alcohol of embodiment 1	100
The polyvalent alcohol of embodiment 2			100
					The polyvalent alcohol of embodiment 4			100
Water		4.0	4.0	4.0
					V.1	1.0	1.0	1.0
IV.1		0.15	0.15	--
					IV.2	0.05	0.05	0.05
IV.3		0.18	0.185	0.19
					T80	51.4	51.4	50.3
Index		108	108	108
					Pore structure	Tiny	Tiny	Cracking
Tap density	[kg/m ³]	25	25

Tensile strength	[kPa]	65	61
				Elongation at break	[%]	82	78
Compressive strength	[kPa]	3.1	3.1
				CS90%	[%]	7.2	27.7

Listed result shows that the polyester ether polylol that only has described in the embodiment of the invention 1 and 2 shows good processing characteristics in the table 1.

Component A-4 by the inventive method (step (i)) and the preparation of non-method of the present invention, A-5 and A-6:

The preparation of component A-4 (with 0.50mol sulfuric acid/mol KOH neutralization)

Step (i-1):

The aqueous sorbitol solution of 237.1g70% is injected the 2L autoclave with the 0.516g KOH aqueous solution (KOH that contains 44.9wt.%).Under agitation (800rpm) dewaters in a vacuum until in the temperature that is issued to 150 ℃ less than 10 millibars absolute pressure.Then under 100 millibars to 120 millibars absolute pressure by passing into the 50ml nitrogen/minute content of reactor is swept and to be blown 2 hours.Under 150 ℃, in 2.93 hours, 363.2g propylene oxide metering ground is added.In this case, obtain the absolute total pressure of 5.0 bar., be cooled to room temperature and add 790g soya-bean oil by uncapping of reactor after 1.07 hours at secondary reaction under 150 ℃ the temperature.By with nitrogen three extraordinarily straightening to 3 bar absolute pressure and remove oxygen residual in the reactor by being decompressed to subsequently normal atmosphere.After being heated to 150 ℃, the absolute pressure of 2.5 bar is set with nitrogen, then in 5.48 hours, the stirring velocity metering ground of 181.6g oxyethane with 800rpm is added.After 2.6 hours, it is cooled to 80 ℃ at secondary reaction.

Step (i-2):

And then step (i-1) joins the sulfuric acid of 0.5252g12.16% 474.4g from the product of step (i-1) and stirred 30 minutes under 80 ℃.

Step (i-3):

And then step (i-2) is adding 0.2377g

After 1076, under 8 millibars (absolute pressures), under 110 ℃, dewatered 3 hours.Obtain component A-4.

The preparation of component A-5 (with 0.919mol sulfuric acid/mol KOH neutralization)

With such as comparative example's 8 described steps (i-1) of carrying out.

Step (i-2):

And then step (i-1) adds the sulfuric acid of 0.9483g12.16% 466.2g from the product of step (i-1) and stirred 30 minutes under 80 ℃.

Step (i-3):

And then step (i-2) is adding 0.2420g

After 1076, under 8 millibars (absolute pressures), under 110 ℃, dewatered 3 hours.Obtain component A-5.

The preparation of component A-6 (with 1.255mol sulfuric acid/mol KOH neutralization)

With such as comparative example's 8 described steps (i-1) of carrying out.

Step (i-2):

And then step (i-1) joins 1.4311g12.16% sulfuric acid 514.9g from the product of step (i-1) and stirred 30 minutes under 80 ℃.

Step (i-3):

And then step (i-2) is adding 0.2584g

After 1076, under 8 millibars (absolute pressures), under 110 ℃, dewatered 3 hours.Obtain component A-6.

(contrast) embodiment 8-10: according to the step of present method (ii) component A-4, A-5 and The conversion of A-6

Use propylene oxide and oxyethane as B component 1)

The comparative example 8: according to the conversion of the step component A-4 (ii) of present method

Be infeasible with the conversion of carrying out the step component A-4 (ii) according to the present invention with the mode of the step described in the similar embodiment 9, because in 3 hours, the activation of dmc catalyst do not occur.Therefore do not transform in (ii) in step.

Embodiment 9: according to the conversion of the step component A-5 (ii) of present method

In the 10L autoclave, drop into 300.1g component A-5 and 0.033g B component 2), under agitation (450rpm, trellis agitator) is heated to 130 ℃.Under this temperature, under the absolute pressure of＜0.1 bar, sweep by nitrogen and blow 30 minutes.Under agitation subsequently, under 130 ℃, the mixture metering ground that amounts to 686.8g propylene oxide and 76g oxyethane is added in the reactor.Be the purpose of deactivated catalyst, at first only then this mixture of 30g interrupted metering with the amount adding of metering.After 39 minutes, descend to indicate the initial activation of catalyzer at original measurement by the acceleration of pressure in the reactor, so that the epoxide of residual content is without interruption in 2.53 hours.Until behind the constant pressure, be cooled to 90 ℃ and under the vacuum pressure of 10 millibars absolute pressure, volatile part was removed subsequently in 30 minutes after epoxide metering finishes and continuous 0.33 hour of secondary reaction.

Adding 0.551g

After 1076, obtaining the OH value is the end product of the clarification of 56.5mg KOH/g.

The comparative example 10: according to the conversion of the step component A-6 (ii) of present method

Be infeasible with the conversion of carrying out the step component A-6 (ii) according to the present invention with the mode of the step described in the similar embodiment 9, because in 3 hours, the activation of dmc catalyst do not occur.Therefore do not transform in (ii) in step.

Conclusion:

Only the intermediate product (component A-5) by the inventive method neutralization can transform (embodiment 9) with epoxy alkane further in DMC-catalytic step subsequently.For non-step according to the inventive method (comparative example 8 and 10), the activation of dmc catalyst does not occur, so the conversion of intermediate product (component A-4 and A-6) and epoxy alkane does not occur.

Claims

1. for the preparation of the method based on reproducible raw-material polyester ether polylol (1), it has 3mg to less than component A) the OH value of OH value, described method is characterised in that:

(i) have at least component A of the OH value of 70mg KOH/g) prepare by following steps:

(i-1) in the presence of basic catalyst, the initial compounds A1 of H-official's energy) with one or more fatty acid esters A2) and one or more epoxy alkane A3) transform, the relative concentration of contained basic catalyst is in component A) total mass count 40ppm to 5000ppm, and subsequently

(i-2) with the product of sulfuric acid neutralization from step (i-1), it is characterized in that the catalyzer that uses in every mole of step (i-1) uses 0.75mol to 1mol sulfuric acid, and be characterised in that the salt that produces is retained in component A in this process) in, and

(ii) subsequently in double metal cyanide (DMC) catalyst B 2) in the presence of, component A) with one or more epoxy alkane B1) transform.

2. according to claim 1 method is characterized in that after step (i-2), in step (i-3) in the removal of the trace water that carries out reaction water under 1 millibar to 500 millibars the absolute pressure and under 20 ℃ to 200 ℃ the temperature and introduce with acid.

3. according to claim 1 and 2 method, it is characterized in that step (ii) in, will the initiator polyvalent alcohol and dmc catalyst drop in the reactor system and supply continuously component A) and one or more epoxy alkane B1).

4. according to claim 3 method, it is characterized in that step (ii) in, with the component A of part amount) or the polyester ether polylol (1) of the previous separately preparation according to the present invention as the initiator polyvalent alcohol.

5. according to claim 1 and 2 method, it is characterized in that step (ii) in, will be from the component A of whole amounts of step (i)) and dmc catalyst drop into, and supply continuously one or more H-officials can initial compounds and one or more epoxy alkane B1).

6. according to claim 1 and 2 method, it is characterized in that step (ii) in, the dmc catalyst of initiator polyvalent alcohol and part amount is dropped in the reactor system, and supply continuously component A) and one or more epoxy alkane B1) and dmc catalyst, and the polyester ether polylol (1) that forms discharged from reactor continuously.

7. according to claim 6 method, it is characterized in that step (ii) in, with the component A of part amount) or the polyester ether polylol (1) of the previous separately preparation according to the present invention as the initiator polyvalent alcohol.

8. method one of according to claim 1-7 is characterized in that epoxy alkane to be metered into contains at least 10% oxyethane in the step (i).

9. method one of according to claim 1-8, it is characterized in that in step (i-1), at first will treat all to be supplied to one or more epoxy alkane A3 of the 5wt.%-95wt.% amount of step (i-1)) can initial compounds A1 with H-official) transform, amount with metering adds one or more fatty acid esters A2 subsequently), then will treat all to be supplied to one or more epoxy alkane A3 of the 95wt.%-5wt.% amount of step (i-1)) add and initiation reaction with the amount of metering.

10. method one of according to claim 1-9 is characterized in that described dmc catalyst uses in the concentration with respect to the amount 10ppm-1000ppm of polyester ether polylol (1).

11. method one of according to claim 1-10 is characterized in that isolating dmc catalyst after the epoxy alkane addition has finished.

12. method one of according to claim 1-11 is characterized in that described one or more fatty acid esters A2) hydroxyl group not.

13. the polyester ether polylol that one of can be according to claim 1-12 obtains.

14. polyester ether polylol according to claim 13 is for the preparation of the purposes of urethane purpose.

15. contain the urethane of the polyester ether polylol of claim 13.